US10538448B2 - Process for waste confinement by vitrification in metal cans - Google Patents

Process for waste confinement by vitrification in metal cans Download PDF

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US10538448B2
US10538448B2 US12/737,617 US73761709A US10538448B2 US 10538448 B2 US10538448 B2 US 10538448B2 US 73761709 A US73761709 A US 73761709A US 10538448 B2 US10538448 B2 US 10538448B2
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mass
process according
glass
waste
oxidizing agent
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US20110144408A1 (en
Inventor
Philippe Gruber
Olivier Pinet
Hélène Rabiller
Roger Boen
Nicolas Bousquet
Jean-Luc Dussossdy
Jacques Lacombe
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/005—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture of glass-forming waste materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/20—Agglomeration, binding or encapsulation of solid waste
    • B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
    • B09B3/29—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix involving a melting or softening step
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/06—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in pot furnaces
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping

Definitions

  • This invention relates to a process for waste confinement, containment, by vitrification in a metal can.
  • the process according to the invention is an improvement to vitrification waste confinement processes that use a hot metal can as the production crucible.
  • the technical field of the invention may thus be defined in general as the treatment of waste or effluents by confinement, coating or immobilisation.
  • the technical field of the invention is waste confinement by vitrification and more precisely by vitrification in hot metal cans.
  • This waste may be solid waste, or liquid waste particularly in the form of solutions.
  • It may be nuclear waste, but it could also be any industrial or household waste that contains mineral species, and particularly polluting metals and/or polluting metallic ions.
  • waste might include solid residues from the incineration of household waste, particularly residues formed by boiler ash, fly ash and filtration cakes originating from the neutralisation and treatment of incineration exhaust gases.
  • the metal can is poured into a container in which it is cooled, and the process is called “hot crucible” process, or the metal can is taken out of the furnace and then cooled and used as a container for the final glass, and the process is then called “in-can melting” method.
  • This disclosure applies to the latter type of method.
  • Confinement, containment, glasses produced industrially at the present time such as confinement glass for nuclear waste or household waste incineration residues are derived from formulation studies that optimise their compositions and even their production temperatures, if the production temperature is not already fixed by constraints related to the process or to the composition of the glass.
  • composition and temperature optimisations are aimed at obtaining a glass formulation that can:
  • existing processes for the vitrification of nuclear wastes such as fission products usually include two steps, firstly evaporation-calcination of fission product solutions to obtain a calcine, cullet, followed by vitrification of the calcine, cullet formed.
  • the evaporation-calcination step may be carried out in a rotating tube heated in a resistance furnace. This process is known to the man skilled in the art.
  • the confinement glass is a borosilicate glass composed mainly of about 80% of SiO 2 (silica), B 2 O 3 (boric oxide), Al 2 O 3 (alumina) and Na 2 O (sodium oxide).
  • vitrification additive such as a glass frit
  • the role of the vitrification additive is simply to provide elements so that once they have been mixed with the waste, will result in confinement of the waste in a glass with the required properties, some of which were mentioned above.
  • Measures used in the past to limit chemical interactions with the glass bath, corrosion of the metal can and loss of its integrity used a combination of several actions, namely a limited temperature of the glass bath, a very short residence time of the glass bath in the hot metal can, and the use of special steels to provide good resistance to corrosion.
  • Degassing usually means the leaving of chemical elements in the form of gas from the glass bath.
  • Foaming usually means the accumulation of bubbles on the surface of the molten glass bath.
  • Foaming may cause molten glass to spill outside the melting can.
  • Foaming is a possible consequence of the degassing phenomenon in the glass bath.
  • the purpose of this invention is to provide a process for waste confinement, containment by vitrification in a heated metal can that satisfies inter alia these needs.
  • Another purpose of this invention is to provide a process for waste confinement by vitrification in a heated metal can that does not have the disadvantages, defects, limitations and drawbacks of the processes for waste confinement by vitrification in a heated metal can according to the prior art, particularly in terms of volatilisation, degassing and foaming, and that provides a solution to the problems of the processes according to the prior art.
  • the purpose of this invention is to overcome problems specific to metal can, “in-can” processes, particularly corrosion and foaming due to the volatilisation of species in the glass bath reduced by the melting can.
  • a process for confining a waste containing at least one chemical species to be confined, by vitrification in a heated metal can wherein the waste and a vitrification additive are fed into the metal can, the waste and the vitrification additive are melted to obtain a glass melt, and the glass melt is cooled, characterised in that at least one oxidising agent is further fed into the metal can and in that the concentration of oxidising agent(s) expressed as oxide(s) in the glass melt is from 0.1 to 20% by mass, preferably from 4 to 20% by mass, more preferably from 5 to 15% by mass, and even more preferably from 10 to 13% by mass of the mass of the glass melt.
  • the inventors have identified, and that had never been done before, the cause of volatilisation and foaming problems that occur in heated metal cans, and have surprisingly provided a solution to these problems by feeding, according to the invention, an oxidising agent into the metal can in addition to the waste and to the vitrification additive.
  • the inventors have shown that the degassing (gas freeing) and foaming phenomena were actually due to the reduction of some species present in the molten glass bath under the action of the metal can, this reduction creating volatile reduced forms at the working temperature of the process.
  • glass formulations are based on oxides and are often of the silicate or borosilicate type.
  • many of said elements can exist in different states of oxidation, namely Fe 3+ / 2+ / 0 , Zn 2+ /Zn 0 , Cd 2+ /Cd, Cr 6+ /Cr 3+ /Cr 2+ /Cr 0 , S 6+ / 4+ / 0 / ⁇ 2 , Ni 2+ / 0 , Mn 3+ / 2+ / 0 , Mo 6+ / 5+ / 4+ / 3+ / 0 , Cs + /Cs 0 . . . .
  • the can can act as a powerful reducing agent reducing the glass bath and multivalent elements contained in it.
  • metallic elements of the metal can are oxidised and diffuse in the glass. Reduction phenomena vary depending on the residence time at high temperature, the temperatures involved, the composition of the glass and the nature of the metals used for the metal cans.
  • degassing and foaming are the result of the volatilisation of some species in the molten glass bath for which the reduced form is volatile at the working temperature of the process, for example approximately 1100° C.
  • the working temperature of the process for example approximately 1100° C.
  • this is the case for cadmium and zinc for which the boiling temperatures of the metal forms are 767° C. and 907° C. respectively, and for other species such as caesium.
  • feeding of an oxidising agent into the heated metal can quantitatively mitigate, counteract, the reduction reactions of elements such as the multivalent elements of the glass, by the metal can.
  • Document FR-A-2 888 576 discloses the reduction of foaming phenomena in molten glass used to vitrify fission products using a reducing frit as a vitrification additive, but the process disclosed in this document is not specifically a vitrification process in a heated metal can according to the meaning of the present invention.
  • the teachings of said document cannot be used for vitrification in a heated metal can.
  • the cause of the foaming mentioned in the document is fundamentally different from the cause of the foaming found by the inventors with vitrification in metal can, namely the departure of oxygen in the form of bubbles due to an excessively oxidising medium.
  • this document does not specifically concern vitrification in a metal can, nor problems specific to this process in a metal can such as corrosion and foaming related to volatilisation of species of the glass bath which are reduced by the melting can. It does not mention nor suggest any solution for solving these problems.
  • the oxidising agent(s) may be chosen from among multivalent oxidising agents.
  • the oxidising agent(s) is (are) thus chosen from among multivalent oxidising species (with a high oxidisation level) of iron, chromium, vanadium, antimony, titanium, arsenic, cerium, manganese, chromium, ruthenium and mixtures thereof.
  • the oxidising agent(s) is (are) chosen from among Fe 3+ , Ce 4+ , Mn 4+ , Sb 5+ , As 5+ , V 5+, Ru 4+ , and mixtures thereof.
  • the oxidising agent(s) such as the multivalent oxidising species may be in the form of their oxides, or precursors of these oxides.
  • the at least one oxidising agent is an agent that has a limiting effect on the corrosion of the metal can, such as Fe 2 O 3 .
  • the concentration of oxidising agent(s) expressed as oxide(s) in the glass melt may usually be from 0.1 to 20% by mass, preferably 4 to 20% by mass, more preferably 5 to 15% by mass and even more preferably 10 to 13% by mass, of the glass melt.
  • the concentration of the oxidising agent may thus be from 0.1% to 1% by mass for Cr 3+ , expressed as Cr 2 O 3 ; from 1 to 15% by mass for V 5+ , expressed as V 2 O 5 ; from 0.5 to 7 or 8% by mass for Sb 5+ , expressed as Sb 2 O 5 ; from 1 to 15% by mass for Ti 4+ , expressed as TiO 2 ; from 0.5 to 7 or 8% by mass for As 5+ , expressed as As 2 O 5 ; from 0.5 to 10% by mass for Ce 4+ , expressed as CeO 2 ; from 0.1 to 2% by mass for Mn 4+ , expressed as MnO 2 ; and from 1 to 20%, preferably from 1 to 15%, more preferably from 3 to 13%, better from 4 or 5 to 13%, or still better from 10 to 13% by mass, and preferably from 12 to 13% by mass, for example 12.6% by mass for Fe 3+
  • the at least one oxidising agent may be fed in the form of a powder composed preferably of a mixture of oxide powders and/or the oxidising agent may be fed in the form of a glass containing this element, oxidising agent, for example in the form of a glass frit, of glass beads, or glass pieces.
  • the at least one oxidising agent may be mixed with the waste before the waste is fed into the metal can.
  • the oxidising agent may be mixed or chemically incorporated into the vitrification additive before they are fed into the metal can.
  • the oxidising agent may be fed directly into the metal can, separately from the waste and the vitrification additive.
  • Two or more of said methods,of feeding the oxidising agent may be combined.
  • the oxidising agent may be fed into the metal can continuously, or the oxidising agent may be fed into the metal can discontinuously.
  • the metal can be made from an iron-based alloy such as a steel, for example a stainless steel, or a nickel-based alloy such as inconel.
  • the vitrification additive may be in the form of a mixture of oxide powders or it may be in the form of a glass, for example a glass frit, glass beads, or pieces of glass.
  • the vitrification additive may include oxides chosen from among SiO 2 (silica), B 2 O 3 (boric oxide), Al 2 O 3 (alumina), Na 2 O (sodium oxide), Fe 2 O 3 , CaO, Li 2 O, ZnO, ZrO 2 , etc.
  • the vitrification additive may be a borosilicate glass or a silicate glass.
  • the chemical element(s) to be confined, contained may be chosen from among the following chemical elements: Al, As, B, Ba, Ca, Ce, Cd, Cr, Cs, F, Fe, Gd, Hg, Li, Mg, Mn, Mo, Na, Ni, Nd, P, Pb, S, Sb, Tc, Ti, V, Zn, Zr, actinides such as Pu, platinoids, their isotopes, particularly their radioactive isotopes, and mixtures thereof.
  • the waste treated by the process according to the invention may be solid or liquid.
  • This waste may in particular be a solid or liquid nuclear waste.
  • the nuclear waste may be a radioactive liquid effluent such as a radioactive solution.
  • the nuclear waste could be a cullet, calcine of a radioactive liquid effluent, particularly a medium activity effluent.
  • the waste may also be derived from the incineration of radioactive wastes or household wastes.
  • the glass melt may be poured into a container and cooled in it, or the glass melt may be cooled in the metal can in which it was prepared.
  • the single FIGURE is a schematic cross sectional view of a device for carrying out the process according to the invention.
  • FIG. 1 shows a metal container or can ( 1 ) for implementation of the process according to this invention.
  • This can is usually in the form of a straight, vertical cylinder with a circular cross-section, open in its upper part and comprising a sidewall ( 2 ) and a base ( 3 ).
  • the diameter of this can is generally from 100 mm to 1000 mm and its height is from 100 mm to 1100 mm, and its volume may vary from 1 to 250 L.
  • This can is a metallic can, which means that its wall and its base are usually made from a metal or a metal alloy such as an iron-based alloy, for example a stainless steel, or a nickel-based alloy such as inconel.
  • a metal or a metal alloy such as an iron-based alloy, for example a stainless steel, or a nickel-based alloy such as inconel.
  • This metal or alloy could be coated, depending on the case.
  • One of the advantages of the process according to the invention is that it makes it possible to use common metals and alloys without any particular resistance to corrosion and that are less expensive such as stainless steels, particularly steel grades 309, 310 or 314, while other processes according to the prior art without the addition of oxidising agents in the glass melt usually require metals and alloys with high resistance to corrosion such as work-hardened nickel-based alloys such as inconels, for example type 600 or 601 . . . , and special steels such as “ODS” steels with dispersion of oxides.
  • the metal can is usually heated by putting the can in a medium frequency induction furnace ( 4 ), for example an induction furnace with a 200 kW generator operating at a frequency of 4 kHz.
  • a medium frequency induction furnace 4
  • the glass inside the metal can is then melted by conduction in contact with the metal wall.
  • the can may also be heated in an electrical resistance furnace.
  • Heating is done until melting occurs, in other words it must be sufficient to create a melting bath or glass melt.
  • the temperature of the melting bath must be high enough to cause total melting of the vitrification additive and of the oxidising agent, and to incorporate the waste to be confined. This temperature depends on the vitrification additive, the oxidising agent and the wastes to be confined.
  • the vitrification additive is a borosilicate glass frit
  • the glass frit, oxidising agent and wastes mixture may usually be heated to a temperature of 900 to 1300° C., for example 1100° C. or 1200° C.
  • the vitrification additive is fed into the metal can through a duct ( 5 ) connected to the upper part of the metal can.
  • This vitrification additive ( 6 ) is usually chosen from among mixtures of oxide powders, and preferably from among glasses, but also from among glass precursors such as carbonates, nitrates, oxides, borides, nitrides, carbides, metals, sulphates, sulphides, hydroxides, etc., and mixtures thereof.
  • the glass may be in different forms: for example, it may be in flakes called “glass frit”, beads, or even glass pieces.
  • the vitrification additive for example the glass frit or precursors of it, may be in a physicochemical form like those currently used to introduce confinement glass in one of the waste confinement processes by vitrification known in the prior art.
  • the vitrification additive used such as a glass frit may for example include various oxides, namely SiO 2 (silica), B 2 O 3 (boric oxide), Al 2 O 3 (alumina), Na 2 O (sodium oxide), Fe 2 O 3 , CaO, Li 2 O, ZnO, ZrO 2 , etc.
  • the vitrification additive may be a borosilicate glass or a silicate glass.
  • the vitrification additive such as a glass frit
  • the vitrification additive is preferably a silicate glass.
  • it may be glass for example in the form of a glass frit comprising principally about 80% of SiO 2 (silica), B 2 O 3 (boric oxide), Al 2 O 3 (alumina) and Na 2 O (sodium oxide).
  • it may be a glass frit comprising from 20 to 80% or from 20 to 75% by mass of SiO 2; from 0 to 40% or from 0 to 25% by mass of B 2 O 3 , from 0 to 20% of Fe 2 O 3 ; from 0 to 25% by mass of Na 2 O; from 0 to 25% or from 0 to 20% by mass of Al 2 O 3 ; from 0 to 20% or from 0 to 15% by mass of CaO; from 0 to 20% or from 0 to 10% by mass of Li 2 O; from 0 to 20% by mass of ZnO; and from 0 to 20% or from 0 to 15% by mass of ZrO 2 .
  • borosilicate glass may be cited for example the so-called “R7T7” glass that is very frequently used for vitrification of fission products, and for which the composition is known.
  • the waste ( 7 ) containing the chemical element(s) to be confined is fed into the metal can ( 1 ).
  • This waste is introduced into the metal can through the same pipe ( 5 ) shown in the single figure, but it could be introduced through a different, separate channel.
  • the waste and the vitrification additive may be fed simultaneously or successively.
  • the element(s) to be confined is (are) not particularly limited and may be chosen from among the following chemical elements—Al, As, B, Ba, Ca, Ce, Cd, Co, Cr, Cs, F, Fe, Gd, Hg, La, Li, Mg, Mn, Mo, Na, Ni, Nd, P, Pb, S, Sb, Tc, Te, Ti, V, Zn, Zr, actinides such as Pu, platinoids, isotopes of said chemical elements, in particular radioactive isotopes of said chemical elements, and mixtures thereof.
  • chemical elements Al, As, B, Ba, Ca, Ce, Cd, Co, Cr, Cs, F, Fe, Gd, Hg, La, Li, Mg, Mn, Mo, Na, Ni, Nd, P, Pb, S, Sb, Tc, Te, Ti, V, Zn, Zr, actinides such as Pu, platinoids, isotopes of said chemical elements, in particular radioactive isotopes
  • the waste may be in solid or liquid form, for example in the form of a solution.
  • the process according to the invention is applicable particularly for solid or liquid nuclear waste.
  • This nuclear waste may for example be in the form of radioactive liquid effluents, particularly medium activity radioactive liquid effluents, for example aqueous solutions.
  • radioactive liquid effluents may be nitric aqueous effluents containing metal or metalloid nitrates.
  • the nuclear waste is a solid waste, it may particularly be a cullet, calcine of a radioactive liquid effluent, and particularly of an effluent with medium activity.
  • the calcination step is usually done in a rotating tube, for example heated to 400° C. by an electric furnace.
  • the solid cullet is crushed by a swinging bar located inside the rotating tube heated at the required temperature.
  • a dilution additive or a calcination additive may be added.
  • the waste treated by the process according to the invention may also be a waste derived from incineration of household or radioactive waste.
  • At least one oxidising agent is added into the metal can in addition to the waste and to the vitrification additive.
  • the oxidising agent may be chosen from among nitrates and sulphates associated with a cation that may or may not itself have an oxidising action.
  • the oxidant is iron oxide derived from decomposition of the nitrate or the iron nitrate itself.
  • the iron nitrate produces iron oxide and No x and apparently a synergetic effect occurs between these two compounds that increases their respective effects, particularly their oxidising effects, and boosts their advantages.
  • Nitrates or sulphates when hot, oxidise the glass bath, the glass melt, and enable it to counteract the reduction reactions of the multivalent elements of the glass melt by the metal can.
  • the oxidising agent(s) is (are) chosen from among the multivalent oxidising elements.
  • this or these oxidising agent(s) may be chosen from among multivalent oxidising species of iron, chromium, vanadium, antimony, titanium, arsenic, cerium, manganese, chromium, ruthenium and mixtures thereof.
  • a multivalent oxidising species usually means a multivalent species with a high degree of oxidation, namely usually greater than or equal to 2 and possibly as high as 6, for example equal to 2, 3, 4, 5 or 6.
  • the multivalent oxide species used will be the one with the highest degree of oxidisation, for example in the Fe(III)/Fe(II) redox pair, the Fe(III) species will be used in the process according to the invention.
  • the oxidising agent(s) is (are) chosen from among Fe 3+ , Ce 4+ , Mn 4+ , V 5+ , Sb 5+ , As 5+ , Ru 4+ and mixtures thereof.
  • the oxidising agent(s) such as the multivalent oxidising species mentioned above may be added in chemical form, for example in the form of oxides of these species or precursors of these oxides such as nitrates or sulphates.
  • the nitrate or sulphate function performs an oxidising role but it is difficult to determine whether or not the nitrate function has a higher oxidising role than the oxide function.
  • oxides or precursors of these oxides
  • oxides of elements taken in a high oxidising state such as Fe 3+ , Ce 4+ , Mn 4+ , or V 5+
  • these oxides or precursors thereof are embedded, incorporated into the glass and oxidisation reactions occur between them and the glass, that counteract the reduction reactions generated by the metal elements of the can.
  • oxidants added in the form of nitrates or sulphates oxidants added in the form of oxides do not cause degassing, that would then have to be managed during the gas treatment.
  • the oxidising agent may also be chosen from among oxidising agents that do not form part of the composition of the final glass because they disappear completely at the melting temperature of the glass melt, during production of the glass or during confinement, containment.
  • these agents are nitric acid, etc.
  • the oxidising agent is an agent that has a limiting effect on corrosion of the metal can such as Fe 2 O 3 .
  • the process according to the invention not only prevents degassing and foaming phenomena but also prevents corrosion of the hot can.
  • the oxidising agent may be fed into the metal can in any appropriate form.
  • the oxidising agent may be fed in the form of a powder, particularly when it is an oxide, for example a powder composed of a mixture of oxides.
  • the oxidising agent may also be fed in the form of a glass, and particularly of a glass frit.
  • the oxidising agent may be mixed with waste before the waste is fed into the metal can, and/or the oxidising agent may be mixed with the vitrification additives before they are fed into the metal can and/or the oxidising agent may be fed directly into the metal can, separately from the waste and vitrification additives.
  • the oxidising agent may be chemically incorporated into the vitrification additive which is in the form of glass, and particularly a glass frit, before it is fed into the can.
  • the vitrification additives are fed in the form of glass, particularly glass flakes
  • the oxidising agent(s) may be fed into this additive glass to give it an oxidising capacity.
  • the oxidising agent may be fed into the metal can continuously or discontinuously.
  • the vitrification additives and the waste may be fed continuously or discontinuously.
  • the oxidising agent, waste and vitrification additives may be fed in a single step or in several steps.
  • oxidising agents such as the multivalent oxidising elements and their contents should be determined as a function of:
  • the nature and quantity of oxidising agent to be used can be determined empirically for each type of waste.
  • the waste, oxidising agent and the vitrification additive may be fed into the metal can in any order, in sequence; they may all be fed at the same point (for example through the duct 5 ) or at different points; and two or all three of them may be fed simultaneously into the reaction vessel through the same path or through different paths.
  • the process according to the invention could have a global duration for example of the order of 20 to 120 hours with waiting phases or holding phases at high temperatures, for example at 900 to 1200° C., for a duration from a few minutes (for example 2, 5, 10 minutes) to several tens of hours (for example 20, 30, 50, 100 hours).
  • the process according to the invention may comprise 2 to 5 feed phases lasting for 4 to 12 hours each followed by a waiting, holding phase, of the glass melt at a high temperature, each with a duration of 10 to 14 hours.
  • the process according to the invention is fully adaptable, completely variable in terms of its global duration and the nature, number, duration and conditions of the various phases.
  • the glass melt may be cast in a container different from the metal can and cooled in the metal can, or the glass melt may be cooled in the metal can (in-can melting).
  • the device shown in the single figure comprises a duct ( 8 ) to release gases from the metal can and to transfer them to a gas treatment installation (not shown).
  • vitrification of wastes is done in metal cans (in-can melting) in an installation complying more or less with the scheme in FIG. 1 .
  • the volume of the metal can, container, used in all the examples is about 50 litres.
  • a mixture of wastes and vitrification additives is continuously fed into the metal can during the feed phases, each lasting for about 12 hours.
  • the wastes are in the form of a nitric aqueous solution containing the chemical species to be confined.
  • These species are Li, S, Zr, F, Na (with 50% by mass of the solution), Cd (with 15% by mass of the solution), Fe, Ca, Cr, Al, Mg, Nd and Zn (with 10% by mass of the solution).
  • the wastes solution is fed at a flow rate of about 5 L/h.
  • vitrification additives that will provide oxides complementary to the waste oxides, to achieve the final glass composition, are added in the examples in the form of glass flakes called “glass frit” at a flow rate of about 2.5 kg/h.
  • One of the special features of the tests done in the following examples is the alternation between 12-hour continuous feed phases and standby phases in which the temperature is held for about 12 hours. These two phases are alternated until the can is full and contains about 110 kg of glass.
  • the can is separated from the rest of the process.
  • composition of the wastes solution is always the same and is as defined above, and the flow rate is the same.
  • vitrification additives without the addition of an oxidising additive or with the addition of various types of oxidising additives.
  • the glass reduction for each example is estimated by measuring the oxygen pressure in the molten glass at 1100° C. using an electrochemical system such as a “Rapidox” furnace sold by “Glass-Service®”.
  • Foaming, degassing, the formation of metal particles and sulphur balls, beads, and corrosion of the metal can are observed for each example.
  • This example is an example nonconforming with the invention in which no oxidising additives are added into the vitrification additive.
  • the can is a 316L stainless steel can.
  • the vitrification additive is composed of the following oxides, without any addition of oxidising additives: SiO 2 62.5%, B 2 O 3 19.5%; Li 2 O 1.89%; ZrO 2 3.42%; Na 2 O 7.59%; Al 2 O 3 3.51%.
  • the measured oxygen pressure is 10 ⁇ 10 atmospheres.
  • Cadmium has partially vaporised, volatilized, the cadmium content analysed in the glass is 1.52% by mass compared with 2.67% expected.
  • the waste solution is the same as in example 1.
  • the can is a 310 stainless steel can (NS30).
  • the vitrification additive used is a frit containing 3% by mass of iron, predominantly with oxidation degree +III that gives it a slightly oxidising capacity.
  • the iron oxide is added into the frit in order to provide acceptable properties to the material for its production in the process.
  • the vitrification additive contains 3% by mass of Fe 2 O 3 as the oxidising agent and a preparation containing 3.6% by mass of Fe 2 O 3 in the glass melt is targeted, since part of the Fe 2 O 3 originates from the waste.
  • composition by mass of the glass frit that makes up, constitutes the vitrification additive is SiO 2 60%, B 2 O 3 19%; Li 2 O 2%; ZrO 2 2%; Na 2 O 7%; Fe 2 O 3 3%; CaO 2%; Al 2 O 3 3%; Nd 2 O 3 2%.
  • the oxygen pressure increases to 10 ⁇ 9.3 atmosphere.
  • the glass is slightly more oxidised than it is in example 1, which has the consequence of limiting cadmium reduction phenomena to the metal state and consequently reducing degassing phenomena compared with example 1.
  • Corrosion of the can is significant and comparable to that in example 1.
  • This example is an example according to the invention in which oxidising additives are added into the waste solution.
  • the waste solution is the same as that in examples 1 and 2.
  • the can and the glass frit constituting, forming the vitrification additive are the same as those used in example 2, except that 9% additional iron III oxide is also added into the waste solution such that the final glass contains 12.6% by mass of Fe 2 O 3 iron oxide (namely 9%+3.6%).
  • the oxygen pressure in the final glass is considerably higher than in examples 1 and 2 because it is equal to 10 ⁇ 3.1 atmosphere.
  • the metal can is only slightly corroded.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Glass Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
US12/737,617 2008-07-28 2009-07-28 Process for waste confinement by vitrification in metal cans Active US10538448B2 (en)

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FR0855168 2008-07-28
FR0855168A FR2934183B1 (fr) 2008-07-28 2008-07-28 Procede de confinement de dechets par vitrification en pots metalliques.
PCT/EP2009/059735 WO2010012726A1 (fr) 2008-07-28 2009-07-28 Procède de confinement de déchets par vitrification en pots métalliques

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FR3009642B1 (fr) 2013-08-08 2018-11-09 Areva Nc Procede et installation d'incineration, fusion et vitrification de dechets organiques et metalliques
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RU2011107300A (ru) 2012-09-10
JP2011528992A (ja) 2011-12-01
KR101653421B1 (ko) 2016-09-01
KR20110055556A (ko) 2011-05-25
EP2303786A1 (fr) 2011-04-06
FR2934183A1 (fr) 2010-01-29
RU2523844C2 (ru) 2014-07-27
EP2303786B1 (fr) 2017-04-12
CN102164864A (zh) 2011-08-24
US20110144408A1 (en) 2011-06-16
CN102164864B (zh) 2015-07-29
WO2010012726A1 (fr) 2010-02-04
JP5753782B2 (ja) 2015-07-22

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